Color glaze mixed type ink of ceramic ink jet printing anti-electrostatic and preparation method thereof
Technical field
The present invention relates to a kind of technology of ceramic tile decoration, be specially a kind of ceramic ink jet printing ink, more specifically, color glaze mixed type ink relating to a kind of ceramic ink jet printing anti-electrostatic and preparation method thereof.
Background technology
Inkjet technology is a kind of contactless digital printing technologies succeeded in developing late 1970s.It by ink by the nozzle ejection on printhead on various dielectric surface, achieve noncontact, high speed, the monochrome of low noise or the word of colour or image printing.At the beginning of 21 century, Ferro Corporation develops the oil-based ink being adapted at pottery carrying out spray ink Printing, is 00818261.2 at the corresponding number of patent application of China.The widespread use of inkjet technology at architectural pottery production field is started with this.As a kind of brand-new ceramic decoration theory, ceramic decoration colour print technology can make full use of abundant computer data, digital technique is incorporated in traditional architectural pottery product, ceramic decoration is made to closely follow era step, embody stylistic features, meet the requirement of people's personalization, ceramic decoration technology is pushed to a new stage.
Inkjet technology tool compared with the traditional decoration means of ceramic tile production has the following advantages: (1) energy-saving and emission-reduction, product has been broken away from batch production needs film-making, screen cloth, the intermediate step such as mechanical, shorten and change the line of production the cycle, significantly enhance productivity, also reduce the loss in the process of changing the line of production; (2) print procedure is completely by computer control, complicated pattern decorative can be carried out in production process, and the precision of pattern improves with repeatable, greatly can improve mechanization degree and the production efficiency of decoration process, also can complete the short run even customization of single products; (3) contactless, can print on male and fomale(M&F), make the decoration of some special-shaped products become easy, extreme enrichment decorative effect.
But ink-jet printed technique belongs to a kind of surface decoration technique, namely predetermined pattern is formed at ceramic tile surface by printing of inkjet printer, main component at present in disclosed ink set is tinting material/colorant and solvent, and makes tinting material/colorant additive such as homodisperse dispersion agent in a solvent.The printed layer that spray ink Printing is formed is how not wear-resisting, even after high temperature sintering, is easier to wearing and tearing in the printed layer of ceramic tile surface yet, and therefore need executes layer of transparent protection glaze to protect printed layer more.This make the production cost of ink-jet printed series ceramic Wall or floor tile and the production cycle all very high.
Electrostatic protection is that a lot of special engineering needs to consider at present, and the material of construction that the fields such as such as aerospace, precision manufactureing, microelectronics, weaving use all needs good electrostatic protection performance.And the printed layer that the ink of spray ink Printing is formed at present does not have electrostatic protection effect substantially, be not therefore suitable for and produce the use of anti-electrostatic class fictile.
Summary of the invention
The object of the invention is to color glaze mixed type ink proposing a kind of ceramic ink jet printing anti-electrostatic and preparation method thereof, when using ceramic ink jet printing color glaze mixed type ink provided by the invention to produce ceramic wall and floor bricks product, ink-jet printed rear direct high temperature burns till, without the need to after executing transparency protected glaze again after ink-jet printed again high temperature burn till, Glaze Composition in ink is meeting melting when burning till, and the chromophoe constituent in ink is dispersed in wherein uniformly, and then make ink-jet printed layer wear-resisting especially; Additionally by interpolation conductor oxidate, when burning till, form the melts of conduction, and then the printed layer that spray ink Printing is formed also has good anti-static effect.
For reaching this object, the present invention by the following technical solutions: a kind of color glaze mixed type ink of ceramic ink jet printing anti-electrostatic, comprising various components be by mass percentage: colorant: 25% ~ 30%; Powdered frit: 10% ~ 15%; Magnesiumcarbonate: 1% ~ 5%; Glycol ether: 45% ~ 55%; Dispersion agent: 1% ~ 3%; Bonding agent: 0.5% ~ 2%; Tensio-active agent: 0.5% ~ 2%; Conductor oxidate: 5% ~ 10%.
In above-mentioned ink, conductor oxidate is preferably one or more combinations in stannic oxide, zinc oxide, titanium oxide, Cadmium oxide; Because Cadmium oxide has stronger toxicity, titanium oxide has considerable influence to ink colour generation, therefore, and one or both combinations more preferably in stannic oxide, zinc oxide.
Going for high temperature to make ink to burn till, preferably, is one or more combinations in praseodymium yellow, reddish brown, orange, cobalt blue, spinel system black pigment at the colorant described in the color glaze mixed type ink of above-mentioned a kind of ceramic ink jet printing anti-electrostatic.
After making sintering, the printed layer using ink provided by the invention to be formed has good texture, preferably, the chemical composition mass percent of the powdered frit described in the color glaze mixed type ink of above-mentioned a kind of ceramic ink jet printing anti-electrostatic is: silicon-dioxide: 45% ~ 50%; Aluminum oxide 18% ~ 22%, ferric oxide :≤0.2%; Titanium dioxide :≤0.3%; Calcium oxide 8% ~ 12%; Magnesium oxide 4% ~ 5%; Potassium oxide: 2% ~ 5%; Sodium oxide: 3% ~ 5%; Barium oxide: 2% ~ 4%; Zirconium white: 1% ~ 2%; Loss on ignition :≤1%; Water :≤0.5%.
The color glaze mixed type ink of above-mentioned a kind of ceramic ink jet printing anti-electrostatic is weakly alkaline; It is minimum to the corrodibility of shower nozzle when its PH is between 7 ~ 8.
In the color glaze mixed type ink of above-mentioned a kind of ceramic ink jet printing anti-electrostatic during solid content >=50%, there is particularly preferred hair color effect.
The present invention also provides a kind of preparation method of color glaze mixed type ink of above-mentioned a kind of ceramic ink jet printing anti-electrostatic: it comprises the steps:
The siccative mixing of step 1) colorant and powdered frit; Be that 25 ~ 30:10 ~ 15:5 ~ 10 take by the mass ratio of colorant, powdered frit, conductor oxidate, then pour in quick mixer and mix.
Step 2) comminution by gas stream; The colorant adopting high speed jet mill to mix step 1) and powdered frit compound carry out beating powder, obtain the ultrafine powder that particle diameter reaches 10 μm ~ 50 μm.
Step 3) batching and one-level ball milling; Be in mass ratio: 40 ~ 55:1 ~ 5:45 ~ 60 take step 2) ultrafine powder, magnesiumcarbonate, the glycol ether that obtain, then pour into aluminum oxide be ball lining and ball ball mill in ball milling, Ball-milling Time 12 ~ 24 hours, obtains the mixed slurry that particle diameter is 1 ~ 10 μm.
Step 4) batching and secondary ball milling; Be mixed slurry, dispersion agent, bonding agent, the tensio-active agent that the ratio of 86 ~ 120:1 ~ 3:0.5 ~ 2:0.5 ~ 2 takes step 3) and obtains in mass ratio, pour double planetary high speed ball mill into grind, milling time 4 ~ 10 hours, obtains ink work in-process.
Step 5) constant-temperature vacuum filters; Ink work in-process step 4) obtained, in the constant temperature a mixing bowl of 80 ~ 100 DEG C, then carry out vacuumizing, vibration at high speed, use aperture≤10 μm strainer filtering, obtain ink.
Preferably, in the preparation method of the color glaze mixed type ink of above-mentioned a kind of ceramic ink jet printing anti-electrostatic, the colorant described in step 1) be reach that 325 order standard analysiss tail over≤0.05% through 700 ~ 850 DEG C of temperature lower calcinations, granularity, the powdery praseodymium yellow of moisture content≤0.5%, one or more combinations in reddish brown, orange, cobalt blue, spinel system black pigment.
Preferably, in the preparation method of the color glaze mixed type ink of above-mentioned a kind of ceramic ink jet printing anti-electrostatic, glaze described in step 1) is silicon-dioxide 45 ~ 50 for selecting chemical composition mass ratio: aluminum oxide 18 ~ 22: ferric oxide 0 ~ 0.2: titanium dioxide 0 ~ 0.3: calcium oxide 8 ~ 12: magnesium oxide 4 ~ 5: potassium oxide 2 ~ 5: sodium oxide 3 ~ 5: barium oxide 2 ~ 4: the raw material of zirconium white 1 ~ 2 is through 700 ~ 850 DEG C of calcinings, calcination time 1 ~ 3 hour, obtains the grog of loss on ignition≤1%, moisture content≤0.5%.
In order to avoid introducing impurity, obtain good grinding effect, with stable drop mass, in a kind of preparation method of color glaze mixed type ink of ceramic ink jet printing anti-electrostatic, the ball mill performance requriements used in step 3) is as follows: ball adopts isostatic pressing process, diameter 10 ~ 35mm; The Chemical Composition mass percent of ball lining, ball is: aluminium sesquioxide >=95%, silicon-dioxide 2% ~ 5%, ferric oxide≤0.1%, volume density >=3.7 gram/cc of ball lining, ball, ball milling cycle abrasion≤0.1 ‰ of ball lining, ball, Mohs' hardness >=9.5.
In order to avoid introducing impurity, obtain good grinding effect, with stable drop mass, in a kind of preparation method of color glaze mixed type ink of ceramic ink jet printing anti-electrostatic, in the double planetary high speed ball mill used in step 4), the material of ball grinder and ball is zirconium white.
Select the disclosed technique of application publication number CN103113133A, preparation adobe, then selects the color glaze mixed type ink of ceramic ink jet printing anti-electrostatic provided by the invention to carry out ink-jet printed in adobe, forms printed layer, then enters klining.Test the ceramic tile obtained, test shows, the body resistance of adobe is 2 ~ 8 × 10
7Ω, substantially identical with public data in CN103113133A; The surface resistivity of printed layer is 3 × 10 in addition
7~ 5 × 10
8Ω, therefore ink disclosed by the invention has good anti-static effect, is applicable to prepare anti-static ceramic goods.
Compared with the existing technology scheme provided by the invention has following advantage:
1, ink complete processing is simple, practical, after ink jet unit spray ink Printing, does not need in printed layer, impose one deck ink protection glaze again.Burnt till by kiln, after color glaze mixed type ink sintering, self can form one deck printed layer wear-resisting closely, which greatly simplifies the production technique of spray ink Printing decoration, and reduce production cost, enhance productivity.
2, the printed layer that ink is formed has good anti-static effect, and the anti-static ceramic goods utilizing it to produce are applicable to special engineering purposes.
3, magnesiumcarbonate is introduced in color glaze mixed type ink set; play outside the suspension stability of enhancing ink, anti-caking effect effect; because it is in alkalescence; in the course of processing, react with closing in the acid colorants generation soda acid in ink, and make ink be weakly alkaline; the acid ink made compared with prior art is compared; be more conducive to the protection (acidity can corrode expensive printing head) of ink jet unit printhead, extend the work-ing life of shower nozzle, cost-saving.
4, color glaze mixed type ink solids content is high, and granularity is less, and hair color effect is better than existing ink.
5, color glaze mixed type ink adopt solvent be glycol ether (boiling point is 245 DEG C), there is not the problem of solvent evaporates, to the mankind and environment safer.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
Embodiment 1-5
The component formula of the ceramic ink jet printing color glaze mixed type ink that embodiment 1-5 provides is as following table 1.
Table 1
The colorant selected in embodiment 1 is praseodymium yellow, and prepared ink colour generation is yellow.Conductor oxidate is the mixture of stannic oxide and zinc oxide, and the mass ratio of stannic oxide and zinc oxide is 8:2.The chemical composition mass percent of powdered frit is: silicon-dioxide: 45% ~ 50%; Aluminum oxide 18% ~ 22%, ferric oxide :≤0.2%; Titanium dioxide :≤0.3%; Calcium oxide 8% ~ 12%; Magnesium oxide 4% ~ 5%; Potassium oxide: 2% ~ 5%; Sodium oxide: 3% ~ 5%; Barium oxide: 2% ~ 4%; Zirconium white: 1% ~ 2%; Loss on ignition :≤1%; Water :≤0.5%.By above chemical composition mass percent, the chemical analysis results that those skilled in the art commonly use mineral or frit class raw material by Sai Geershi and Production of Ceramics calculates formula consumption, therefore the chemical composition requirement of powdered frit is only gived here, for the raw material of Different sources or the frit of different chemical component, those skilled in the art can arrange in pairs or groups selection flexibly.Here a given concrete powdered frit batch formula: albite 35%, potassium felspar sand 9%, aluminum oxide 6%, Wingdale 10, kaolin 10, burns talcum 10%, barium carbonate 5%, wollastonite 7%, clear frit 3%, zirconium silicate 5%.But need to illustrate, above formula does not form any limitation of the invention.
The ink preparation technology of the present embodiment 1 is as follows:
The present invention also provides a kind of preparation method of color glaze mixed type ink of above-mentioned a kind of ceramic ink jet printing anti-electrostatic: it comprises the steps:
The siccative mixing of step 1) colorant and powdered frit; Be that 25:10:10 takes by the mass ratio of colorant, conductor oxidate, powdered frit, then pour in quick mixer and mix.
Step 2) comminution by gas stream; The colorant adopting high speed jet mill to mix step 1), conductor oxidate, powdered frit compound carry out beating powder, obtain the ultrafine powder that particle diameter reaches 10 μm ~ 50 μm.
Here the principle of work of illustratively comminution by gas stream: micronizer mill and cyclonic separator, fly-ash separator, induced draft fan form a whole set of crushing system.Pressurized air is after filtration after drying, crushing chamber is entered by laval nozzle high-velocity jet, at the joint place material of multiply high pressure draft by impact several times, friction, shearing and pulverizing, material after pulverizing moves to graded region with upstream under blower fan draft effect, under the powerful centrifugal action that the stage turbine of high speed rotating produces, make thickness feed separation, the fine particle meeting granularity requirements enters cyclonic separator and fly-ash separator collection by grading wheel, and coarse particles drops to disintegrating area to be continued to pulverize.Above Jet Mill is known device, can buy obtain in market.
Step 3) batching and one-level ball milling; Be in mass ratio: 45:1:47 takes step 2) ultrafine powder, magnesiumcarbonate, the glycol ether that obtain, then pour into aluminum oxide be ball lining and ball ball mill in ball milling, Ball-milling Time 12 ~ 24 hours, obtains the mixed slurry that particle diameter is 1 μm ~ 10 μm.
In order to avoid introducing impurity, obtain good grinding effect, with stable drop mass, in the present embodiment, the ball mill performance requriements used in step 3) is as follows: ball adopts isostatic pressing process, diameter 10 ~ 35mm; The Chemical Composition mass percent of ball lining, ball is: aluminium sesquioxide >=95%, silicon-dioxide 2% ~ 5%, ferric oxide≤0.1%, volume density >=3.7 gram/cc of ball lining, ball, ball milling cycle abrasion≤0.1 ‰ of ball lining, ball, Mohs' hardness >=9.5.
Step 4) batching and secondary ball milling; In mass ratio for the ratio of 93:3:2:2 takes mixed slurry, dispersion agent, bonding agent, the tensio-active agent that step 3) obtains, pour double planetary high speed ball mill into and grind, milling time 4 ~ 10 hours, obtain ink work in-process.
Dispersion agent is some water-soluble and oil soluble high score subclass, phenylformic acid and derivative, polyacrylic acid and multipolymers thereof etc. mainly.
Bonding agent ensures that the ceramic body of printing or colorant have certain intensity, and be convenient to production operation, stablize the mobility of ink, usual resin can play the dual function of bonding agent and dispersion agent.Resin is divided into the synthetic resins of natural resin and aggretion type, bonding agent in formula adopt polymerization type resin as: a kind of in polyethylene, polypropylene, polyvinyl chloride and polystyrene.
Tensio-active agent is that the surface tension of control ink factory is in the scope be applicable to.As carboxylic acid, sulfonic acid, sulfuric acid, amino or amido and salt thereof.
The principle of work of double planetary ball mill is: on the traffic cycle of one (revolution), be provided with two major planets axles in (rotation), does the running of single file planetary.Two mini-roundabouts are installed again on two major planets axles simultaneously four ball grinder protecting seats (put ball grinder with) are installed on (revolution) two mini-roundabouts make double planetary in (rotation) and operate.Ball grinder is when this running up, and the mill ball in ball grinder defines very large high-frequency percussion power, straight line impact force, friction to material, carries out quick fine grinding to material under the effect of mass force, mixing and dispersed sample.It is known device, can by buying acquisition on the market.
In order to avoid introducing impurity, obtain good grinding effect, with stable drop mass, in the present embodiment 1, in the double planetary high speed ball mill used in step 4), the material of ball grinder and ball is zirconium white.
Step 5) constant-temperature vacuum filters; Ink work in-process step 4) obtained, in the constant temperature a mixing bowl of 80 ~ 100 DEG C, then carry out vacuumizing, vibration at high speed, use aperture≤10 μm strainer filtering, obtain ink.
Certainly, in order to easy to use, in the present embodiment 1, carry out bottling packaging after the ink after step 5) constant-temperature vacuum filters is cooled to room temperature again, can be delivered on ceramic ink jet printing production line and use.
Embodiment 2
Fill a prescription see each constituent mass ratio given in table 1.In the present embodiment, the colorant used is for cobalt blue and spinel system black pigment are in mass ratio for 1:2 mixing is obtained, the ink color that both ratios can be allocated in actual use as required carries out collocation consumption, and also can add other pigment where necessary, such as: praseodymium yellow, reddish brown, orange etc.Conductor oxidate is chosen as the mixture of titanium oxide and stannic oxide, and both mass ratioes are 1:2.
In the present embodiment, preparation method is substantially the same manner as Example 1, and difference is, re-uses after the raw material of the colorant used in the present embodiment carries out calcination process in advance.Be specially: by cobalt blue and spinel system black pigment at 700 ~ 850 DEG C of temperature lower calcinations, and reach that granularity reaches that 325 order standard analysiss tail over≤0.05%, could as the raw material of colorant after moisture content≤0.5%.
The ink color development of preparation like this is more stable compared with the technique of embodiment 1.Because prepare the raw material of colorant after calcining, foreign matter content is wherein less, and mineral composition is also more homogeneous.
Embodiment 3
In the present embodiment, colorant is that reddish brown and orange to be that 1:3 mixes by quality obtained, and Pigment Material also passes through the calcination processing as embodiment 2.Conductor oxidate is chosen as stannic oxide.
In the present embodiment, the raw material preparing powdered frit also needs to carry out calcining rear use.Be specially and the raw material preparing powdered frit is calcined in high temperature silicon carbon bar furnace, calcining temperature 700 ~ 850 DEG C, calcination time 1 ~ 3 hour.So just can obtain the grog of loss on ignition≤1%, moisture content≤0.5%.Use the grog after calcining can stablize ink performance as glaze powder raw material, this is because the raw mineral materials do not calcined wherein has more organism, loss on ignition is higher, the printed layer using the higher raw material of loss on ignition ink can be made to be formed as glaze powder raw material may have more needle pore defect after burning till, cause printed layer crude, affect visual appearance.
The preparation technology of embodiment 4 and embodiment 5 is substantially the same manner as Example 3, and the raw material of prepared colorant is respectively reddish brown and orange, does not just do additionally repeating here.Conductor oxidate is respectively zinc oxide and titanium oxide in mass ratio for 2:3 and zinc oxide and Cadmium oxide are in mass ratio for 4:1 is prepared from.
Need to illustrate, Cadmium oxide has stronger toxicity, and titanium oxide has certain influence to ink color development, and therefore these two kinds of conductor oxidates need prudent use.
Measure the pH value of embodiment 1-5 ink, between 7 ~ 8, in weakly alkaline; And insolubles particle diameter≤10 μm in ink, so surface does not have large corner angle, there is excellent stability and rheological, can not wear and tear, block and corrode shower nozzle, extend the work-ing life of shower nozzle, cost-saving.
Embodiment 6-10
In the present embodiment, select the disclosed technique of application publication number CN103113133A, preparation adobe, the color glaze mixed type ink of the ceramic ink jet printing anti-electrostatic then selecting embodiment of the present invention 1-5 to provide in adobe carries out ink-jet printed, form printed layer, then enter klining, preparation embodiment 6-10 tests the ceramic tile obtained, test shows, the body resistance of adobe is 2 ~ 8 × 10
7Ω, substantially identical with public data in CN103113133A; The surface resistivity of embodiment 6-10 printed layer is 3 × 10
7~ 5 × 10
8Ω, meets the index of correlation of National Standard of the People's Republic of China's " anti-static ceramic tile ".Therefore ink disclosed by the invention has good anti-static effect, is applicable to prepare anti-static ceramic goods.
Comparative example 1
For advantage of the present invention is described, spy provides comparative example 1.The technique as embodiment 6-10 is selected to prepare ceramic tile in the present embodiment, difference to be adopted ink be printed layer that common ink that market sells formed.Test result is as follows:
The body resistance of adobe is 2 ~ 8 × 10
7Ω, substantially identical with public data in CN103113133A; But the surface resistivity of printed layer is about 10
18Ω, does not meet the index of correlation of National Standard of the People's Republic of China's " anti-static ceramic tile ".After adopting current normal ink stamp, brick body does not possess antistatic protection function substantially.
Below know-why of the present invention is described in conjunction with specific embodiments.These describe just in order to explain principle of the present invention, and can not be interpreted as limiting the scope of the invention by any way.Based on explanation herein, those skilled in the art does not need to pay performing creative labour can associate other embodiment of the present invention, and these modes all will fall within protection scope of the present invention.